Modified silane compounds

ABSTRACT

This invention relates to the reversible protection of hydroxy-silane functional groups by acid cleavable protecting groups. The development of reversible protecting groups greatly enhances the current utility of silanes while introducing further novel applications. For instance, reversibly protected silanes are of particular value in applications where room temperature cure and/or adhesion is of value, such as coatings, high resolution imaging, caulks, adhesives, sealents, gaskets, and silicones. Reversibly protected silanes can also be beneficially used in reticulating agents, and in sizing agents, tires, and release coatings. The incorporation of reversibly protected silanes into coating resins is of particular value. The reversibly protected silane can be incorporated into the coating resin by polymerizing a monomer containing the reversibly protected silane into the resin or by post-addition into the coating formulation. The reversibly protected silane remains protected under basic conditions, such as in a coating formulation that contains a volatile base, for instance ammonium hydroxide. However, deprotection occurs under mildly acidic conditions. Thus, as a coating formulation containing a volatile base dries the volatile base evaporates and deprotection occurs. This allows for controlled room temperature crosslinking to occur with hydroxy-functionalized polymers. The present invention more specifically discloses a modified silane compound consisting of a silane having 3 or 4 acetal moieties bonded thereto.

[0001] This is a divisional of U.S. patent application Ser. No.10/222,739, filed on Aug. 16, 2002, which claims the benefit of U.S.Provisional Application Serial No. 60/312,851, filed on Aug. 16, 2001,and U.S. Provisional Application Serial No. 60/326,042, filed on Sep.28, 2001.

BACKGROUND OF THE INVENTION

[0002] Most conventional coating resins are insoluble in water.Therefore, in general practice, they have been dissolved in a suitableorganic solvent or dispersed in water with the aid of an emulsifyingagent or surfactant in order to provide a coating composition suitablefor application to a substrate surface. A serious disadvantage oforganic solvent solutions is that they are potentially toxic, flammableand environmental pollutants. Water-reducible coatings greatly reducethe magnitude of these problems. For this reason, water-based paints arecurrently being used as a replacement for oil-based paints in manyapplications.

[0003] Various water-reducible coating resins, such as the one describedin U.S. Pat. No. 4,474,926, have been developed. Water-reduciblecoatings that utilize such resins have been developed for a variety ofpurposes and have been widely accepted in many applications such ashighway striping paint.

[0004] U.S. Pat. No. 4,968,741 describes a coating for metal substrateswhich provides improved corrosion and rust resistance. Such coatings areof the water-reducible type and can be beneficially utilized in theautomotive industry and other applications where good rust resistance isneeded. For instance, such coatings are excellent for coating bridgesand other outdoor metal structures.

[0005] It is also critical for coatings made with water-reduciblecoating formulations to offer the desired combination of physical andchemical properties. For instance, in many applications, it is importantfor the coating to exhibit excellent flexibility, excellent ultra-violetlight resistance and excellent solvent resistance. In applications whichinvolve metal substrates, outstanding corrosion and rust-resistance isnormally also sought.

[0006] For purposes of this patent application, an aqueous coatingsystem is considered to be a colloidal dispersion of a resin in waterwhich can be reduced by the addition of water and which forms a durablecoating when applied to a substrate surface. The term aqueous coatingsystem is used herein interchangeably with the term water-reduciblecoating. Other names which are sometimes applied to water-reduciblecoatings are water-born, water-solubilized and water-dilutable.

SUMMARY OF THE INVENTION

[0007] This invention relates to the reversible protection ofhydroxy-silane functional groups by acid cleavable protecting groups.The development of reversible protecting groups greatly enhances thecurrent utility of silanes while introducing further novel applications.For instance, reversibly protected silanes are of particular value inapplications where room temperature cure and/or adhesion is of value,such as high resolution imaging, caulks, adhesives, sealents, gaskets,and silicones. Reversibly protected silanes can also be beneficiallyused in reticulating agents, and in sizing agents, tires, and releasecoatings.

[0008] The incorporation of reversibly protected silanes into coatingresins is of particular value. The reversibly protected silane can beincorporated into the coating resin by polymerizing a monomer containingthe reversibly protected silane into the resin or by post-addition intothe coating formulation. The reversibly protected silane remainsprotected under basic conditions, such as in a coating formulation thatcontains a volatile base, for instance ammonium hydroxide. However,deprotection occurs under mildly acidic conditions. Thus, as a coatingformulation containing a volatile base dries the volatile baseevaporates and deprotection occurs. This allows for controlled roomtemperature crosslinking to occur with hydroxy-functionalized polymers.Chemical adhesion to hydroxy-group containing substrates, such as metal,glass, and wood, also occurs. This makes coating resins that containreversibly protected silanes especially valuable for coating metals,glass, and wood. Since such coating formulations that contain reversiblyprotected silanes are curable at room temperature they are much easierto apply and cure than conventional systems. Benefits associated withusing coating formulations that contain reversibly protected silanes arerealized in a wide variety of applications including structuralcoatings, anti-corrosion coatings, and marine biofouling coatings.

[0009] This invention further relates to the synthesis of a latex whichcan be used in making self-crosslinking water-reducible coatingcompositions, such as paints, which offer excellent solvent resistance,reduced drying time and improved adhesion to metal and glass. Coatingswhich are formulated with the latex of this invention areenvironmentally advantageous because they contain no or extremely lowlevels of volatile organic compounds and additionally offer excellentflexibility and excellent ultra-violet light resistance.

[0010] The present invention more specifically discloses awater-reducible coating composition which is comprised of (1) water; (2)a resin having repeat units which are derived from (a) about 30 to about75 weight percent vinyl aromatic monomers, (b) about 20 to about 65weight percent of alkyl acrylate monomers, (c) about 1 to about 8 weightpercent alkyl propenoic acid monomers and (d) about 0.5 to about 5weight percent reversibly protected silane monomers, based on 100 weightpercent monomers; (3) a wetting agent; and (4) a defoamer.

[0011] The subject invention further reveals a process for producing aneutralized latex that is useful in the manufacture ofself-crosslinkable water-reducible coatings which comprises: (1) freeradical aqueous emulsion polymerizing at a pH of less than about 3.5, amonomer mixture which comprises, based on 100 weight percent monomers:(a) from about 30 to about 75 weight percent vinyl aromatic monomers,(b) from about 20 to about 65 weight percent of alkyl acrylate monomers,(c) from about 1 to about 8 weight percent alkyl propenoic acid monomersand (d) about 0.5 to about 5 weight percent reversibly protected silanemonomers; in the presence of about 0.2 to 3 phm of at least one α-olefinsulfonate soap to produce a latex; and (2) neutralizing the latex withammonia to a pH which is within the range of about 7 to about 10.5 toproduce the neutralized latex.

[0012] The present invention also discloses a latex which is useful inthe manufacture of self-crosslinkable water-reducible coatings, saidlatex being comprised of (1) water, (2) an emulsifier and (3) a polymerwhich is comprised of repeat units which are derived from (a) about 30to about 75 weight percent vinyl aromatic monomers, (b) about 20 toabout 65 weight percent of alkyl acrylate monomers, (c) about 1 to about8 weight percent alkyl propenoic acid monomers and (d) about 0.5 toabout 5 weight percent reversibly protected silane monomers.

[0013] The present invention further discloses a modified silanecompound consisting of a silane having 3 or 4 acetal moieties bondedthereto.

[0014] The present invention further discloses a modified silanecompound consisting of silane having 2 acetal moieties bonded theretowith the proviso that the silane compound does not contain a methyl,ethyl, or phenyl group if the silane compound has the followingstructure:

[0015] wherein n represents an integer.

[0016] The present invention further discloses a modified silanecompound having a structural formula selected from the group consistingof:

[0017] wherein n represents an integer from 2 to 4; wherein m representsan integer from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X groups can be the same or different; wherein Xrepresents a chemical moiety; with the proviso that X does not representa methyl group, an ethyl group, or a phenyl group in cases where themodified silane compound is of structural formula (2) wherein nrepresents the integer 1 or the integer 2 wherein R* represents ahydrogen atom wherein Y represents an oxygen atom wherein Z representsthe moiety C(R)R′; wherein R, R′, and R″ can be the same or differentand are selected from the group consisting of hydrogen atoms, alkylgroups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.

[0018] The present invention further discloses a modified silanecompound having a structural formula selected from the group consistingof:

[0019] wherein m represents an integer from 1 to about 20; with theproviso that m can represent the integer 0 for structures of formula (3)wherein Z represents the group C(R)R′ wherein X represents a chemicalmoiety other than a methyl group; wherein X groups can be the same ordifferent; wherein X represents a chemical moiety other than a methyl,ethyl, butyl, or phenyl in cases where the modified silane compound isof structural formula (1) wherein Y represents an oxygen atom wherein Zrepresents the moiety C(R)R′ wherein m in equal to the integer 2 or theinteger 3; wherein X represents a chemical moiety other than a methylgroup, a tertiary butyl group, or a phenyl group in cases where themodified silane compound is of structural formula (3) wherein Yrepresents an oxygen atom wherein Z represents the moiety C(R)R′ whereinm in equal to the integer 3; wherein R, R′, and R″ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) may contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) may be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.

[0020] The present invention further discloses a monomer having astructural formula selected from the group consisting of:

[0021] wherein n represents an integer from 1 to 3; wherein m representsan integer from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X′ groups can be the same or different; wherein X′represents an unsaturated moiety containing at least one non-aromaticdouble bond; wherein R, R′, and R″ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, R″, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon.

[0022] The present invention further discloses a polymer which iscomprised of polymer chains having at least one modified silane moietybonded thereto, wherein said modified silane moiety is of a structuralformula selected from the group consisting of:

[0023] wherein n represents an integer from 1 to 3; wherein m representsan integer from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X″ groups can be the same or different; wherein X″represents a chemical moiety; wherein R, R′, and R″ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.

[0024] The present invention further discloses a modified silanecompound having a structural formula selected from the group consistingof:

[0025] wherein m represents an integer from 1 to about 20; wherein Xgroups can be the same or different; wherein X represents a chemicalmoiety; wherein Q is selected from the group consisting of hydrogenatoms and SiX₃; wherein R and R′ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, and R* can be bonded together in anycombination in cases where R, R′, and R* are not hydrogen atoms, halideatoms, or hydroxy groups; wherein Y represents a moiety selected fromthe group consisting of oxygen, sulfur, nitrogen, and phosphorus;wherein Z represents a moiety selected from the group consisting ofC(R)R′, oxygen, sulfur, nitrogen, and phosphorus; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), and(10) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), and (10) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon.

[0026] The present invention further discloses a monomer having astructural formula selected from the group consisting of:

[0027] wherein m represents an integer from 1 to about 20; wherein X′groups can be the same or different; wherein X′ represents anunsaturated moiety containing at least one non-aromatic double bond;wherein Q is selected from the group consisting of hydrogen atoms andSiX′₃; wherein R and R′ can be the same or different and are selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, alkaryl groups containing from 7 to about 18carbon atoms, alkoxy groups containing from 1 to about 18 carbon atoms,hydroxy groups, and halide atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms, halide atoms, or hydroxygroups; wherein Y represents a moiety selected from the group consistingof oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents amoiety selected from the group consisting of C(R)R′, oxygen, sulfur,nitrogen, and phosphorus; wherein the contiguous cyclic ring in formulas(1), (2), (3), (4), (5), (6), (7), (8), (9), and (10) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), (6), (7), (8), (9), and (10) can be saturated orunsaturated in cases where m represents an integer greater than 1;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon.

[0028] The present invention further discloses a polymer which iscomprised of polymer chains having at least one modified silane moietybonded thereto, wherein said modified silane moiety is of a structuralformula selected from the group consisting of:

[0029] wherein m represents an integer from 1 to about 20; wherein X′groups can be the same or different; wherein X′ represents a chemicalmoiety; wherein Q is selected from the group consisting of hydrogenatoms and X″ ₂Si—; wherein R and R′ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of oxygen, sulfur, nitrogen, and phosphorus;wherein Z represents a moiety selected from the group consisting ofC(R)R′, oxygen, sulfur, nitrogen, and phosphorus; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), and(10) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), and (10) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon.

[0030] The present invention further discloses an acetal compound havinga structural formula selected from the group consisting of:

[0031] wherein M represents an atom selected from the group consistingof Ge, Sn, Pb, Ti, and Zr; wherein n represents an integer from 1 to 4;wherein m represents an integer from 1 to about 20; with the provisothat m can represent the integer 0 for structures of formula (3) whereinZ represents the group C(R)R′; wherein X groups can be the same ordifferent; wherein X represents a chemical moiety; wherein R, R′, and R″can be the same or different and are selected from the group consistingof hydrogen atoms, alkyl groups containing from 1 to about 12 carbonatoms, aryl groups containing from about 6 to about 18 carbon atoms,alkaryl groups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, R″,and R* can be bonded together in any combination in cases where R, R′,R″, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofC(R)R′, oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents amoiety selected from the group consisting of C(R)R′, oxygen, sulfur,nitrogen, and phosphorus; with the proviso that Y and Z can not bothrepresent the moiety C(R)R′; wherein the contiguous cyclic ring informulas (1) and (3) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1) and (3) can be saturated or unsaturated incases where m represents an integer greater than 1; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon.

[0032] The present invention further discloses an acetal compound havinga structural formula selected from the group consisting of:

[0033] wherein M represents an atom selected from the group consistingof Ge, Sn, Pb, Ti, and Zr; wherein m represents an integer from 1 toabout 20; wherein X groups can be the same or different; wherein Xrepresents a chemical moiety; wherein Q is selected from the groupconsisting of hydrogen atoms and MX₃; wherein R and R′ can be the sameor different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, and R* can bebonded together in any combination in cases where R, R′, and R* are nothydrogen atoms, halide atoms, or hydroxy groups; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (1), (2), (3), (4), (5), (6),(7), (8), (9), and (10) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), and(10) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon.

[0034] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal having a structural formula selected from the groupconsisting of:

[0035] wherein m represents an integer from 1 to about 20; wherein R andR′ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein R,R′, and R* can be bonded together in any combination in cases where R,R′, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofoxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:

X_(4−n)SiOR″]_(n)

[0036] wherein n represents an integer from 1 to 4; wherein R″ isselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein X represents a chemical moiety; wherein said process isconducted at a temperature which is within the range of about 10° C. toabout 50° C., wherein said process is conducted at a pressure which iswithin the range of about 25 torr to about 75 torr, and wherein saidprocess is conducted in the presence of an alcohol salt of thestructural formula M′OR′″ wherein M′ represents a Group Ia metal andwherein R′″ represents an alkyl group containing from 1 to 10 carbonatoms.

[0037] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal having a structural formula selected from the groupconsisting of:

[0038] wherein m represents an integer from 1 to about 20; wherein R andR′ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein R,R′, and R* can be bonded together in any combination in cases where R,R′, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofoxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3) , (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:

X_(4−n)SiOR″]_(n)

[0039] wherein n represents an integer from 1 to 4; wherein R″ isselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein X represents a chemical moiety; wherein said process isconducted at a temperature which is within the range of about 10° C. toabout 50° C., wherein said process is conducted at a pressure which iswithin the range of about 25 torr to about 75 torr, and wherein saidprocess is conducted in the presence of an alcohol salt of thestructural formula M′OR′″ wherein M′ represents a Group Ia metal andwherein R′″ represents an alkyl group containing from 1 to 10 carbonatoms.

[0040] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal of the structural formula:

[0041] wherein R and R′ can be the same or different and are selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; with a silicon containing compound of the structuralformula:

X_(4−n)SiOR″]_(n)

[0042] wherein n represents an integer from 1 to 4; wherein R″represents an alkyl group containing from 1 to about 10 carbon atoms,wherein X represents a chemical moiety other than a hydrogen atom or ahalogen; wherein said process is conducted at a temperature which iswithin the range of about 10° C. to about 50° C., wherein said processis conducted at a pressure which is within the range of about 25 torr toabout 75 torr, and wherein said process is conducted in the presence ofan alcohol salt of the structural formula M′OR′″ wherein M′ represents aGroup Ia metal and wherein R′″ represents an alkyl group containing from1 to 10 carbon atoms.

[0043] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal selected from the group consisting of tetrahydropyran-2-oland tetrahydrofuran-2-ol; with a silicon containing compound selectedfrom the group consisting of tetramethylorthosilicate andtetraethylorthosilicate; wherein said process is conducted at atemperature which is within the range of about 10° C. to about 50° C.,wherein said process is conducted at a pressure which is within therange of about 25 torr to about 75 torr, and wherein said process isconducted in the presence of an alcohol salt of the structural formulaM′OR′″ wherein M′ represents a Group Ia metal and wherein R′″ representsan alkyl group containing from 1 to 2 carbon atoms.

[0044] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal having a structural formula selected from the groupconsisting of:

[0045] wherein m represents an integer from 1 to about 20; wherein R andR′ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein R,R′, and R* can be bonded together in any combination in cases where R,R′, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofoxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:

X_(4−n)SiX*]_(n)

[0046] wherein n represents an integer from 1 to 4; wherein X*represents a halide atom; wherein X represents a chemical moiety;wherein said process is conducted in the presence of an amine containingcompound.

[0047] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal having a structural formula selected from the groupconsisting of:

[0048] wherein m represents an integer from 1 to about 20; wherein R andR′ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein R,R′, and R* can be bonded together in any combination in cases where R,R′, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofoxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:

X_(4−n)SiX*]_(n)

[0049] wherein n represents an integer from 1 to 4; wherein X*represents a halide atom; wherein X represents a chemical moiety;wherein said process is conducted in the presence of an amine containingcompound.

[0050] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a cyclichemiacetal of the structural formula:

[0051] wherein R and R′ can be the same or different and are selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; with a silicon containing compound of the structuralformula:

X_(4−n)—Si—X*_(n)

[0052] wherein n represents an integer from 1 to 4; wherein X*represents a halide atom; wherein X represents a chemical moiety;wherein said process is conducted in the presence of an amine containingcompound.

[0053] 22. A process for synthesizing a modified silane which comprisesreacting a vinyl ether compound having a structural formula selectedfrom the group consisting of:

[0054] wherein m represents an integer from 1 to about 20; wherein R,R′, and R″ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R, R′, and R″ can be bonded together in anycombination in cases where R, R′, and R″ are not hydrogen atoms, halideatoms, or hydroxy groups; wherein the contiguous cyclic ring in formulas(2) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (2) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon; with a silicon containing compound ofthe structural formula:

X_(4−n)SiOR*]_(n)

[0055] wherein n represents an integer from 3 to 4; wherein R* isselected from the group consisting of alkyl groups containing from 1 toabout 12 carbon atoms, aryl groups containing from about 6 to about 18carbon atoms, and alkaryl groups containing from 7 to about 18 carbonatoms; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;wherein X represents a chemical moiety; wherein said process isconducted in the presence of an acid.

[0056] The present invention further discloses a process forsynthesizing a modified silane which comprises reacting a ester compoundhaving a structural formula selected from the group consisting of:

[0057] wherein m represents an integer from 1 to about 20; wherein R,R′, and R″ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting of alkylgroups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein thecontiguous cyclic ring in formulas (2) can contain heteroatoms selectedfrom the group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon in cases where m represents an integer greater than 1; whereinthe contiguous cyclic ring in formulas (2) can be saturated orunsaturated in cases where m represents an integer greater than 1;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; with asilicon containing compound of the structural formula:

X_(4−n)SiX*]_(n)

[0058] wherein n represents an integer from 2 to 4; wherein X* isleaving group selected from the group consisting of halide atoms,triflate, and tosylate; wherein X represents a chemical moiety; whereinsaid process is conducted in the presence of the reducing agentdiisobutylaluminum hydride; wherein said process is conducted in thepresence of an amine containing compound.

[0059] The present invention further discloses an aqueous polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an acid; (2) a volatile base; wherein theamount of volatile base present is sufficient for the aqueous polymercomposition to have a pH greater than 7; (3) water; (4) a resin havingrepeat units which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, (b) a monomer in accordance ofclaim 7; (5) a wetting agent; (6) a defoamer; and (7) a pigment, filler,and extender; with the proviso that the aqueous polymer composition canbe void of said wetting agent, defoamer, pigment, filler, and extender.

[0060] The present invention further discloses an aqueous polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an acid; (2) a volatile base; wherein theamount of volatile base present is sufficient for the aqueous polymercomposition to have a pH greater than 7; (3) water; (4) a resin havingrepeat units which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, (b) a monomer in accordance ofclaim 11; (5) a wetting agent; (6) a defoamer; and (7) a pigment,filler, and extender; with the proviso that the aqueous polymercomposition can be void of said wetting agent, defoamer, pigment,filler, and extender.

[0061] The present invention further discloses an aqueous polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an acid; (2) a volatile base selected from thegroup consisting of NR¹R²R³R⁴OH; wherein R¹, R², R³, and R⁴ can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms; R¹, R², R³, and R⁴ can be bondedtogether in any combination in cases where R¹, R², R³, and R⁴ are nothydrogen atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein the amount of volatile base present is sufficient forthe aqueous polymer composition to have a pH greater than 7; (3) water;(4) a resin having repeat units which are derived from (a) a memberselected from the group consisting of vinyl monomers, vinyl aromaticmonomers, conjugated diolefin monomers, and acrylic monomers, (b) amonomer having a structural formula selected from the group consistingof:

[0062] wherein n represents an integer from 1 to 3; wherein m representsan integer from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X′ groups can be the same or different; wherein X′represents an unsaturated moiety containing at least one non-aromaticdouble bond; wherein R, R′, and R″ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, R″, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; (5) a wetting agent; and (6) a defoamer.

[0063] The present invention further discloses a n aqueous polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an acid; (2) a volatile base selected from thegroup consisting of NR¹R²R³R⁴OH; wherein R¹, R², R³, and R can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R¹, R², R³,and R⁴ can be bondedtogether in any combination in cases where R¹, R², R³, and R⁴ are nothydrogen atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein the amount of volatile base present is sufficient forthe aqueous polymer composition to have a pH greater than 7; (3) water;(4) a resin having repeat units which are derived from (a) a memberselected from the group consisting of vinyl monomers, vinyl aromaticmonomers, conjugated diolefin monomers, and acrylic monomers, and (b) amonomer having a structural formula selected from the group consistingof:

[0064] wherein n represents an integer from 1 to 3; wherein m representsan integer from 1 to about 20; wherein X′ groups can be the same ordifferent; wherein X′ represents an unsaturated moiety containing atleast one non-aromatic double bond; wherein R, R′, and R″ can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R, R′, and R″ can be bonded together in any combination in caseswhere R, R′, and R″ are not hydrogen atoms, halide atoms, or hydroxygroups; wherein the contiguous cyclic ring in formula (1) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formula (1) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;(5) a wetting agent; and (6) a defoamer.

[0065] The present invention further discloses an aqueous polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an acid (2) a volatile base selected from thegroup consisting of NR¹R²R³R⁴OH; wherein R¹, R², R³, and R⁴ can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R¹, R², R³, and R⁴ can bebonded together in any combination in cases R′, R², R³, and R⁴ are nothydrogen atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein the amount of volatile base present is sufficient forthe aqueous polymer composition to have a pH greater than 7; (3) water;(4) a resin having repeat units which are derived from (a) a memberselected from the group consisting of vinyl monomers, vinyl aromaticmonomers, conjugated diolefin monomers, and acrylic monomers, and (b) amonomer consisting of the following structure:

[0066] and (5) a wetting agent; and (6) a defoamer.

[0067] The present invention further discloses an organic solvent basedpolymer composition suitable for use as an adhesive, caulk, sealant, orcoating which is comprised of (1) an organic solvent; (2) an acid; (3) avolatile base selected from the group consisting of NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient for the organic solvent basedpolymer composition to be rendered basic; (4) a resin having repeatunits which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, and (b) a monomer having astructural formula selected from the group consisting of:

[0068] wherein n represents an integer from 1 to 3; wherein m representsan integer from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X′ groups can be the same or different; wherein X′represents an unsaturated moiety containing at least one non-aromaticdouble bond; wherein R, R′, and R″ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, R″, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; (5) a wetting agent; and (6) a defoamer.

[0069] The present invention further discloses an organic solvent basedpolymer composition suitable for use as an adhesive, caulk, sealant, orcoating which is comprised of (1) an organic solvent; (2) an acid; (3) avolatile base selected from the group consisting NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient for the organic solvent basedpolymer composition to be rendered basic; (4) a resin having repeatunits which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, and (b) a monomer having astructural formula selected from the group consisting of:

[0070] wherein n represents an integer from 1 to 3; wherein m representsan integer from 1 to about 20; wherein X′ groups can be the same ordifferent; wherein X′ represents an unsaturated moiety containing atleast one non-aromatic double bond; wherein R, R′, and R″ can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R, R′, and R″ can be bonded together in any combination in caseswhere R, R′, and R″ are not hydrogen atoms, halide atoms, or hydroxygroups; wherein the contiguous cyclic ring in formula (1) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formula (1) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;(5) a wetting agent; and (6) defoamer.

[0071] The present invention further discloses an organic solvent basedpolymer composition suitable for use as an adhesive, caulk, sealant, orcoating which is comprised of (1) an organic solvent; (2) an acid; (3) avolatile base selected from the group consisting of NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient for the organic solvent basedpolymer composition to be rendered basic; (4) a resin having repeatunits which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, and (b) a monomer consisting ofthe following structure:

[0072] and (5) a wetting agent; and (6) a defoamer.

[0073] The present invention further discloses a one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition comprising (1) silanol end-terminated organopolysiloxanebase polymer; (2) modified silane compound of claim 3; (3) an acid; (4)a volatile base selected from the group consisting NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient to render the one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition basic; and (5) a reinforcing particulate filler.

[0074] The present invention further discloses a one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition comprising (1) silanol end-terminated organopolysiloxanebase polymer; (2) modified silane compound of claim 9; (3) an acid; (4)a volatile base selected from the group consisting NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient to render the one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition basic; and (5) a reinforcing particulate filler.

[0075] The present invention further discloses a one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition comprising (1) silanol end-terminated organopolysiloxanebase polymer; (2) modified silane compound of claim 12 and claim 13; (3)an acid; (4) a volatile base selected from the group consistingNR¹R²R³R⁴OH; wherein R¹, R², R³, and R⁴ can be the same or different andare selected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms; wherein R¹, R², R³, and R⁴ can be bonded together in anycombination in cases where R¹, R², R³, and R⁴ are not hydrogen atoms;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; whereinthe amount of volatile base present is sufficient to render theone-component condensation-crosslinking room-temperature vulcanizablesilicone rubber composition basic; and (5) a reinforcing particulatefiller.

[0076] The present invention also reveals a process for synthesizing amodified silane which comprises reacting the salt of a cyclic hemiacetalhaving a structural formula selected from the group consisting of:

[0077] wherein A represents an alkali metal atom selected from the groupconsisting of lithium, sodium, and potassium; wherein m represents aninteger from 1 to about 20; wherein R and R′ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, and alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (1), (2), (3), (4), and (5) cancontain heteroatoms selected from the group consisting of oxygen,sulfur, nitrogen, phosphorus, and silicon in cases where m represents aninteger greater than 1; wherein the contiguous cyclic ring in formulas(1), (2), (3), (4), and (5) can be saturated or unsaturated in caseswhere m represents an integer greater than 1; wherein said alkyl groups,aryl groups, alkaryl groups, and alkoxy groups can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; with a silicon containing compound of thestructural formula:

R″_(4−n)SiA′_(n)

[0078] wherein n represents an integer from 1 to 4; wherein R″ isselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; whereinA′ represents a halide atom selected from the group consisting offluorine, chlorine, bromine, and iodine; wherein said process isconducted at a temperature which is within the range of about −100° C.to about 50° C.

[0079] The subject invention further discloses a process forsynthesizing a modified silane which comprises reacting the salt of ahemiacetal having a structural formula selected from the groupconsisting of:

[0080] wherein A represents an alkali metal atom selected from the groupconsisting of lithium, sodium, and potassium; wherein m represents aninteger from 1 to about 20; wherein R and R′ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, and alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (1), (2), and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1), (2),and (3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:

R″_(4−n)SiA′_(n)

[0081] wherein n represents an integer from 1 to 4; wherein R″ isselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; whereinA′ represents a halide atom selected from the group consisting offluorine, chlorine, bromine, and iodine; wherein said process isconducted at a temperature which is within the range of about −100° C.to about 50° C.

[0082] The present invention also reveals a process for synthesizing amodified silane which comprises reacting the salt of a cyclic hemiacetalof the structural formula:

[0083] wherein A represents an alkali metal atom selected from the groupconsisting of lithium, sodium, and potassium; wherein R and R′ can bethe same or different and are selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; with asilicon containing compound of the structural formula:

R″_(4−n)SiA′_(n)

[0084] wherein n represents an integer from 1 to 4; wherein R″represents an alkyl group containing from 1 to about 10 carbon atoms;wherein A′ represents a halide atom selected from the group consistingof fluorine, chlorine, bromine, and iodine; wherein said process isconducted at a temperature which is within the range of about −100° C.to about 50° C.

[0085] The subject invention also discloses a process for synthesizing amodified silane which comprises reacting the sodium salttetrahydropyran-2-ol; with silicon tetrachloride; wherein said processis conducted at a temperature which is within the range of about −100°C. to about 50° C.

[0086] The present invention further discloses a process forsynthesizing the alkali metal salt of a cyclic hemiacetal whichcomprises reacting the cyclic hemiacetal with an alkali metal compoundhaving a structural formula selected from the group consisting of:

R**M*

[0087] wherein M* is an alkali metal selected from the group consistingof Li, Na, and K; wherein R** is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein saidalkyl groups, aryl groups, and alkaryl groups can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; wherein said process is conducted in theabsence of protic solvents selected from the group consisting of R″OH;wherein R″ is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein said alkyl groups,aryl groups, and alkaryl groups can contain heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein said process is conducted at a temperature which iswithin the range of about −100° C. to about 100° C.

[0088] The subject invention also discloses a process for synthesizingthe sodium salt of a cyclic hemiacetal which comprises reacting thecyclic hemiacetal with sodium hydride; wherein said process is conductedin the absence of protic solvents selected from the group consisting ofR″OH; wherein R″ is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein said alkylgroups, aryl groups, and alkaryl groups can contain heteroatoms selectedfrom the group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein said process is conducted at a temperature which iswithin the range of about −100° C. to about 100° C.

[0089] The subject invention also reveals a process for synthesizing thesodium salt of tetrahydropyran-2-ol which comprises reactingtetrahydropyran-2-ol with sodium hydride; wherein said process isconducted in the absence of protic solvents selected from the groupconsisting of R″OH; wherein R″ is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein saidalkyl groups, aryl groups, and alkaryl groups can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; wherein said process is conducted at atemperature which is within the range of about −100° C. to about 100° C.

DETAILED DESCRIPTION OF THE SYNTHESIS OF A COATING RESIN

[0090] The coating resins of this invention are prepared by free radicalemulsion polymerization. The charge compositions used in the preparationof the latices of the coating resins contain monomers, at least oneemulsifier (soap), such as an α-olefin sulfonate surfactant, and atleast one free radical initiator. The monomer charge composition used insuch polymerizations will typically be comprised of (a) from about 30 toabout 75 weight percent vinyl aromatic monomers, (b) from about 20 toabout 65 weight percent of alkyl acrylate monomers, (c) from about 1 toabout 8 weight percent alkyl propenoic acid monomers, and (d) about 0.5to about 5 weight percent of a reversibly protected silane monomer.

[0091] It is preferred for the polymer being synthesized to be comprisedof from about 40 weight percent to about 70 weight percent vinylaromatic monomers, from about 25 weight percent to about 55 weightpercent alkyl acrylate monomers, from about 1.5 weight percent to about5 weight percent alkyl propenoic acid monomers and from about 1 weightpercent to about 3 weight percent of a reversibly protected silanemonomer. It is more preferred for the polymer to be comprised of fromabout 63 weight percent to about 67 weight percent vinyl aromaticmonomers, from about 27 weight percent to about 31 weight percent alkylacrylate monomers, from about 2 weight percent to about 4 weight percentalkyl propenoic acid monomers, and from about 1.5 weight percent toabout 2 weight percent reversibly protected silane monomers.

[0092] Some representative examples of vinyl aromatic monomers which canbe used include styrene, alpha-methyl styrene and vinyl toluene. Styreneand alpha-methyl styrene are the preferred vinyl aromatic monomers. Dueto its relatively low cost, styrene is the most preferred vinyl aromaticmonomer.

[0093] The alkyl acrylate monomers which can be employed have alkylmoieties which contain from 2 to about 10 carbon atoms. The alkylacrylate monomer will preferably have an alkyl moiety that contains from3 to 5 carbon atoms. Normal-butyl acrylate is a highly preferred alkylacrylate monomer.

[0094] The alkyl propenoic acid monomers that can be used have thestructural formula:

[0095] wherein R represents a hydrogen atom or an alkyl group containingfrom 1 to 4 carbon atoms. The R group can accordingly be represented bythe formula —C_(n)H_(2n+1) wherein n is an integer from 0 to 4. Somerepresentative examples of alkyl propenoic acid monomers which can beused include: acrylic acid, methacrylic acid (2-methylpropenoic acid),2-ethylpropenoic acid, 2-propylpropenoic acid and 2-butylpropenoic acid.The preferred alkyl propenoic acid monomers are acrylic acid andmethacrylic acid.

[0096] In most cases, it is advantageous to use a combination of bothacrylic acid and methacrylic acid as the unsaturated carbonyl compoundcomponent used in making the latex. For instance, the utilization ofabout 1 to about 3 weight percent acrylic acid with about 0.5 to about1.5 weight percent methacrylic acid results in the latex having improvedfreeze-thaw stability. For example, the utilization of about 2 percentacrylic acid with 1 percent methacrylic acid as the unsaturated carbonylcompound component results in the latex produced being capable ofwithstanding more than five (5) freeze-thaw cycles. It is important forlatices which are shipped through cold regions of the world to have thisimproved freeze-thaw stability.

[0097] The reversibly protected silane monomers that can be used are ofa structural formula selected from the group consisting of:

[0098] wherein m represents an integer from 1 to about 20; wherein X′groups can be the same or different; wherein X′ represents anunsaturated moiety containing at least one non-aromatic double bond;wherein Q is selected from the group consisting of hydrogen atoms andSiX′₃; wherein R and R′ can be the same or different and are selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, alkaryl groups containing from 7 to about 18carbon atoms, alkoxy groups containing from 1 to about 18 carbon atoms,hydroxy groups, and halide atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms, halide atoms, or hydroxygroups; wherein Y represents a moiety selected from the group consistingof oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents amoiety selected from the group consisting of C(R)R′, oxygen, sulfur,nitrogen, and phosphorus; wherein the contiguous cyclic ring in formulas(1), (2), (3), (4), (5), (6), (7), (8), (9), and (10) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), (6), (7), (8), (9), and (10) can be saturated orunsaturated in cases where m represents an integer greater than 1;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon.

[0099] Some specific examples of reversibly protected silane monomersthat can be used include 3-methacryloxypropylsilane tri-acetal andvinylmethylsilane diacetal.

[0100] The charge composition used in the preparation of the latice willcontain a substantial quantity of water. The ratio between the totalamount of monomers present in the charge composition and water can rangebetween about 0.2:1 and about 1.2:1. It is generally preferred for theratio of monomers to water in the charge composition to be within therange of about 0.8:1 and about 1.1:1. For instance, it is verysatisfactory to utilize a ratio of monomers to water in the chargecomposition of about 1:1.

[0101] The charge composition will also typically contain from about 0.2phm (parts per hundred parts of monomer) to about 3 phm of at least oneemulsifier (soap), such as an α-olefin sulfonate soap. It is normallypreferred for α-olefin sulfonate surfactants to be present in thepolymerization medium at a level within the range of about 0.4 phm toabout 2 phm. It is generally more preferred for the charge compositionto contain from about 0.5 phm to about 1 phm of the α-olefin sulfonatesoap.

[0102] The use of larger amounts of the α-olefin sulfonate soap in thepolymerization medium leads to better latex stability. However, theutilization of larger amounts of surfactant also leads to greaterblushing in the ultimate coating and consequently less rust andcorrosion resistance.

[0103] The free radical aqueous emulsion polymerizations used inpreparing the latice is typically initiated with at least one freeradical generator. The free radical generator is normally employed at aconcentration within the range of about 0.01 phm to about 1 phm. Thefree radical initiators which are commonly used include the variousperoxygen compounds such as potassium persulfate, ammonium persulfate,benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumylperoxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, laurylperoxide, cumene hydroperoxide, p-menthane hydroperoxide, t-butylhydroperoxide, acetyl peroxide, methyl ethyl ketone peroxide, succinicacid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, t-butylperoxymaleic acid, t-butyl peroxybenzoate, acetyl cyclohexyl sulfonylperoxide and the like; the various azo compounds such as2-t-butylazo-2-cyanopropane, dimethyl azodiisobutyrate,azodiisobutylronitrile, 2-t-butylazo-1-cyanocyclohexane,1-t-amylazo-1-cyanocyclohexane and the like, the various alkylperketals, such as 2,2-bis-(t-butyl-peroxy)butane and the like.Water-soluble peroxygen-free radical initiators are especially useful insuch aqueous polymerizations.

[0104] The emulsion polymerization is typically carried out at thetemperature ranging between about 125° F. (52° C.) and 190° F. (88° C.).At temperatures above about 190° F. (88° C.), alkyl acrylate monomers,such as butyl acrylate, have a tendency to boil. Thus, a pressurizedjacket would be required for heating such alkyl acrylate monomers totemperatures in excess of about 88° C. On the other hand, thepolymerization reaction proceeds at a very slow rate at temperaturesbelow about 125° F. (52° C.). The slow rate of polymerizationexperienced at temperatures below about 125° F. (52° C.) results in thepolymer having a nonuniform distribution of repeat units in itsbackbone. The slow rates of polymerization experienced at such lowtemperatures are also undesirable because they greatly reduce thethroughput of the polymerization reactor.

[0105] It is generally preferred for the polymerization temperature tobe maintained within the range of about 150° F. (66° C.) to 180° F. (82°C.). It is generally more preferred for the reaction temperature to becontrolled within the range of about 160° F. (71° C.) to about 170° F.(77° C.). It is important for the polymerization to be conducted at a pHthat is below about 3.5 so that a water-sensitive polymer is notproduced. It is preferred for the pH of the polymerization medium to bemaintained at a level of about 3.0 or less throughout thepolymerization. As the polymerization proceeds, the pH of thepolymerization medium will drop naturally. Thus, good results can beattained by adjusting the pH of the initial monomer charge compositionto within the range of about 3.0 to about 3.5 and allowing thepolymerization to proceed. In such a case, the final pH of thepolymerization medium will be about 1.5 which is highly satisfactory.

[0106] In commercial operations, it is typically desirable to add about15 percent to about 25 percent of the monomers in an initial charge. Theinitial charge is then allowed to react for a period of about 30 minutesto about 60 minutes. Then the balance of the monomers to be charged canbe continuously charged into the reaction zone at a rate which issufficient to maintain a reaction temperature within the desiredtemperature range. By continuously adding the monomers to the reactionmedium while maintaining a relatively constant reaction temperature,very uniform polymers can be prepared.

[0107] In accordance with the process of this invention, the latexsynthesized is then neutralized with ammonia to a pH within the range ofabout 7 to about 10.5. It is normally preferred for the latex to beneutralized to a pH within the range of 8 to 10 and more preferred forthe latex to be neutralized to a pH within the range of about 9.0 toabout 9.5. This can be accomplished by simply dispersing ammoniathroughout the latex to produce neutralized latex. The ammonia willnormally be in the form of ammonium hydroxide.

[0108] The latex formed can be diluted with additional water to theconcentration (solids content) that is desired. This latex can be usedin the preparation of water-reducible coatings using techniqueswell-known to those skilled in the art. Generally, various pigments andplasticizers are added to the latex in the preparation of thewater-reducible coating. Poor adhesion is a problem that is sometimesencountered with water-reducible resins. The adhesion of coatings madewith water-reducible resins to substrates can be greatly improved by theaddition of a plasticizer.

[0109] A film-forming, water-reducible composition, such as a paint, canbe prepared by mixing the latex, one or more pigments and a plasticizer.It is not necessary to include a coalescing solvent in the film-forming,water-reducible formulation. For environmental reasons, it is preferrednot to include a coalescing solvent in the formulation. However, a smallamount (0 to about 50 grams per liter) of coalescing solvent can beincluded. In cases where a coalescing solvent is employed, it ispreferable for it to be at least water-miscible and even more preferablefor it to be water-soluble. Of the various coalescing solvents generallyester-alcohols, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,are preferred.

[0110] It should be noted that the pigment, plasticizer and optionallythe coalescing solvent can be mixed directly with the resin in its wateremulsion or latex. In such an operation, the composite wouldautomatically be in a water-reduced form when sufficient ammonia isused.

[0111] Paint formulations can be made utilizing the latices of thisinvention. Such paint formulations are comprised of one or more pigmentsand the latex (water, emulsifier system and resin). Such paints canoptionally contain fillers, plasticizers, stabilizers, defoamers,dryers, fungicides, insecticides, antifouling agents and anticorrosiveagents.

[0112] Pigments are normally added to paint formulations to impart colorand hiding power to the coating. Titanium dioxide is an example of awidely-used pigment which imparts hiding power and a white color.Mineral pigments, such as oxides of iron and chromium, organic pigments,such as phthalocyanine, and active anticorrosive pigments, such as zincphosphate, are representative examples of other widely-used pigments.

[0113] Fillers are normally inexpensive materials which are added to thepaint formulation to attain the desired consistency and non-settlingcharacteristics. Fillers can also improve the physical properties ofcoatings, such as resistance to cracking and abrasion. Somerepresentative examples of widely utilized fillers include chalks,clays, micas, forms of barites and talcs, and silica.

[0114] Driers are chemical compounds, such as salts of cobalt, lead,manganese, barium and zinc, which speed up drying. Stabilizers arechemical agents which neutralize the destructive effects of heat andultraviolet light. Fungicides and insecticides are commonly added tointerior and exterior house paints. Antifouling compounds are commonlyadded to marine paints to inhibit marine growth. Plasticizers are agentswhich control the hardness of the film or which impart flexibility.

[0115] Of the various plasticizers, it is desired that one be selectedwhich is liquid at room temperature such as 25° C. and have asufficiently high boiling point, preferably at least 100° C., and evenmore preferably, at least 150° C., so that they do not volatilize fromthe coating composition when applied to a substrate. Plasticizers whichcontain multiple hydroxyl groups should be avoided because their use canlead to instability. The plasticizer should enhance the waterinsolubility of a dried coating of the coalesced resin. Further, theplasticizer, or mixture of plasticizers, must be characterized by beingcompatible with the resin itself. For this characterization, asolubility parameter in the range of about 8 to about 16 is required.Such solubility parameter is of the type described in The Encyclopediaof Polymer Science and Technology, Volume 3, Page 854, 1965, John Wileyand Sons, Inc., which is simply determined by the equation

σ=(ΣF)/V=F/MW/d where

[0116] σ=solubility parameter

[0117] F=sum of the pertinent molar attraction constants of groupsdetermined by Small, P A [(J Appl Chem 3, 71, (1953)]

[0118] V=Molar volume at 25° C.

[0119] MW=molecular weight

[0120] d=density at 25° C.

[0121] Various plasticizers can be used for this purpose. They can, forexample, be of the type listed in the Federation Series on CoatingsTechnology, Unit Twenty-two, entitled “Plasticizers,” published April1974, so long as they fulfill the melting point, boiling point andcompatibility requirements. Some representative examples of preferredplasticizers include: butyl benzyl phthalate, blends of diethyleneglycoldibenzoate and dipropylene glycol dibenzoate, and2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0122] Representative of various plasticizers are cyclic plasticizerssuch as phosphoric acid esters, phthalic anhydride esters andtrimellitic acid esters as well as N-cyclohexyl-p-toluene sulfonamide,dibenzyl sebacate, diethylene glycol dibenzoate, di-t-octylphenylether,dipropane diol dibenzoate, N-ethyl-p--toluene sulfonamide,isopropylidenediphenoxypropanol, alkylated naphthalene, polyethyleneglycol dibenzoate, o-p-toluene sulfonamide, trimethylpentanedioldibenzoate and trimethylpentanediol monoisobutyrate monobenzoate.

[0123] Representative of various acyclic plasticizers are adipic acidesters, azelaic acid esters, citric acid esters, acetylcitric acidesters, myristic acid esters, phosphoric acid esters, ricinoleic acidesters, acetylricinoleic acid esters, sebacic acid esters, stearic acidesters, epoxidized esters, as well as 1,4-butane diol dicaprylate,butoxyethyl pelargonate di [(butoxyethoxy)ethoxy] methane, dibutyltartrate, diethylene glycol dipelargonate, diisooctyl diglycolate,isodecyl nonanoate, tetraethylene glycol di(2-ethylbutyrate),triethylene glycol di(2-ethyl-hexanoate), triethylene glycoldipelargonate and 2,2,4-trimethyl-1,3-pentane diol diisobutyrate.

[0124] Additional various plasticizers, cyclic, acyclic, and otherwise,include chlorinated paraffins, hydrogenated terphenyls, substitutedphenols, propylene glycols, polypropylene glycol esters, polyethyleneglycol esters, melamines, epoxidized soys, oils, melamines, liquid,hydrogenated abietate esters, epoxytallate esters, alkyl phthalyl alkylglycolates, sulfonamides, sebacate esters, aromatic epoxies, aliphaticepoxies, liquid poly(α-methyl styrene), maleate esters, mellitateesters, benzoates, benzyl esters, tartrates, succinates, isophthalates,orthophthalates, butyrates, fumarates, glutarates, dicaprylates,dibenzoates and dibenzyl esters. It is to be appreciated that relativelylow molecular weight polymers and copolymers derived from monoolefinscontaining 4 to 6 carbon atoms, mixtures of diolefins and monoolefinscontaining 4 to 6 carbon atoms as well as such hydrocarbons andhydrocarbon mixtures with styrene and/or α-methyl styrene can also beused.

[0125] The preferred esters are prepared from the reaction of carboxylicand dicarboxylic acids including fatty acids, such as the phthalicacids, benzoic acid, dibenzoic acid, adipic acid, sebacic acid, stearicacid, maleic acid, tartaric acid, succinic acid, butyric acid, fumaricacid and glutaric acid with hydrocarbon diols, preferably saturatedhydrocarbon diols, having about 7 to 13 carbon atoms.

[0126] Representative of various phosphoric acid esters are cresyldiphenyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate,diphenyl octyl phosphate, methyl diphenyl phosphate, tributyl phosphate,triphenyl phosphate, tri(2-butoxyethyl) phosphate, tri(2-chloroethyl)phosphate, tri-2(chloropropyl) phosphate and trioctyl phosphate.

[0127] Representative of various phthalic anhydride esters are butyloctyl phthalate, butyl 2-ethylhexyl phthalate, butyl n-octyl phthalate,dibutyl phthalate, diethyl phthalate, diisodecyl phthalate, dimethylphthalate dioctyl phthalates, di(2-ethylhexyl) phthalate, diisooctylphthalate, di-tridecyl phthalate, n-hexyl n-decyl phthalate, n-octyln-decyl phthalate, alkyl benzyl phthalate, bis(4-methyl-1,2-pentyl)phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate,di(2-butoxyethyl) phthalate, dicyclohexyl isodecyl phthalate,dicyclohexyl phthalate, diethyl isophthalate, di n-heptyl phthalate,dihexyl phthalate, diisononyl phthalate, di(2-methoxyethyl) phthalate,dimethyl isophthalate, dinonyl phthalate, dioctyl phthalates, dicaprylphthalate, di(2-ethylhexyl) isophthalate, mixed dioctyl phthalates,diphenyl phthalate, 2-(ethylhexyl) isobutyl phthalate, butyl phthalylbutyl glycolate, ethyl (and methyl) phthalyl ethyl glycolate,polypropylene glycol bis(amyl) phthalate, hexyl isodecyl phthalate,isodecyl tridecyl phthalate and isooctyl isodecyl phthalate.

[0128] Representative of trimellitic acid esters are triisooctyltrimellitate, tri-n-octyl n-decyl trimellitate, trioctyl trimellitate,tri(2-ethylhexyl) trimellitate, tri-n-hexyl n-decyl trimellitate,tri-n-hexyl trimellitate, triisodecyl trimellitate and triisononyltrimellitate.

[0129] Representative of various adipic acid esters are di[2-(2-butoxyethoxy) ethyl] adipate, di(2-ethylhexyl) adipate, diisodecyladipate, dioctyl adipates (including diisooctyl adipate) n-hexyl n-decyladipate, n-octyl n-decyl adipate and di-n-heptyl adipate.

[0130] Representative examples of sebacic acid esters are dibutylsebacate, di(2-ethylhexyl) sebacate, dibutoxyethyl sebacate, diisooctylsebacate and diisopropyl sebacate.

[0131] Representative examples of azelaic acid esters aredi(2-ethylhexyl) acelate dicyclohexyl acelate, diisobutyl azelate anddiisooctyl azelate. In the practice of this invention, thewater-reducible composition of resin, plasticizer and coalescingsolvent, if used, is water-reduced by neutralizing the carboxyl groupsof the resin with ammonia and mixing with water. The resultingdispersion or solution can generally be characterized by being stablewithout appreciable, if any, precipitation of the resin for a period ofat least thirty (30) days and preferably for a period of at least 365days or more at about 25° C.

[0132] Generally, for the purpose of this invention, about 100 to about400 parts by weight water are used per 100 parts by weight neutralizedresin, although more or less water can usually be used depending onwhether a high or low viscosity dispersion or solution is desired orwhether a high or low solids content is desired. It also depends on thetype and amount of coalescing solvent (if any) and plasticizer used. Thewater-reduced coating composition, as an aqueous dispersion or solution,is applied as a coating onto a suitable substrate such as wood, masonry,various plastics and various metals. The water, ammonia and coalescingsolvent are evaporated from the coating, usually at a temperature in therange of about 20° C. to about 100° C., preferably about 25° C. to about50° C. to leave a substantially water-insoluble coating of the coalescedresin and plasticizer. Generally, such a coating can be prepared andapplied without the need for additional hardening agents or curatives todecrease the water sensitivity.

[0133] Therefore, it is an important feature of this invention that adurable crosslinked coating is formed on a substrate through thepreparation of a particular resin having balanced hydrophilic andhydrophobic elements, preferably with a further balance of hard and softsegments, and the formation of a water-reduced composition of such resinwith a combination of pigment and compatible plasticizer. Thecrosslinking occurs rapidly at ambient temperatures without the need foradding separate curatives or crosslinking agents. Improved adhesion tometal and glass substrates is also attained.

[0134] This invention is illustrated by the following examples that aremerely for the purpose of illustration and are not to be regarded aslimiting the scope of the invention or the manner in which it can bepracticed. Unless specifically indicated otherwise, parts andpercentages are given by weight.

EXAMPLE 1

[0135] General. All reagents were purchased from Gelest unless otherwisenoted and used without further purification. Tetrahydropyran-2-ol wasprepared according to the literature by the acid catalyzed hydrolysis ofdihydropyran (see Bartness J. E.; Hays R. L.; Caldwell G.; J. Am. Chem.Soc. 1981, 103, 1338 and March J. in Advanced Organic Chemistry, FourthEd., Wiley Interscience, N.Y.; p 764). The 0.5 M solution of NaOMe inmethanol was purchased from Aldrich.

[0136] Experiment 1a. Tetrahydropyran-2-ol (25 g, 0.24 mol) andn-octadecyldimethylmethoxysilane (82 g, 0.24 mol) where reacted withstirring in the presence of a methanol solution of NaOMe (1 g, 0.5 M)for 2 h at 30° C. and reduced pressure (50 Torr). Methanol formed in thereaction and from the NaOMe solution were distilled and the reactionproduct neutralized with HCl. The n-octadecyldimethylsilane-acetalcompound was obtained as a colorless liquid by ¹H-NMR, ¹³C-NMR,²⁹Si-NMR.

[0137] Experiment 1b. Tetrahydropyran-2-ol (49 g, 0.48 mol) andvinylmethyldiethoxysilane (39 g, 0.24 mol) where reacted with stirringin the presence of a methanol solution of NaOMe (1 g, 0.5 M) for 2 h at30° C. and reduced pressure (50 Torr). Ethanol formed in the reactionand the methanol from the NaOMe solution were distilled and the reactionproduct neutralized with HCl. The vinylmethylsilane di-acetal monomerwas obtained as a colorless liquid in high purity by ¹H-NMR, ¹³C-NMR,²⁹Si-NMR.

[0138] Experiment 1c. Tetrahydropyran-2-ol (74 g, 0.72 mol) and3-methacryloxypropyltrimethoxysilane (60 g, 0.24 mol) where reacted withstirring in the presence of a methanol solution of NaOMe (1 g, 0.5 M)for 2 h at 30° C. and reduced pressure (50 Torr). Methanol formed in thereaction and from the NaOMe solution were distilled and the reactionproduct neutralized with HCl. The 3-methacryloxypropylsilane tri-acetalmonomer was obtained as a colorless liquid in high purity by ¹H-NMR,¹³C-NMR, ²⁹Si-NMR.

[0139] Experiment 1d. Tetrahydropyran-2-ol (98 g, 0.96 mol) andtetraethylorthosilicate (50 g, 0.24 mol) where reacted with stirring inthe presence of a methanol solution of NaOMe (1 g, 0.5 M) for 2 h at 30°C. and reduced pressure (50 Torr). Ethanol formed in the reaction andthe methanol from the NaOMe solution were distilled and the reactionproduct neutralized with HCl. The silane tetra-acetal compound wasobtained as a colorless liquid in high purity by ¹H-NMR, ¹³C-NMR,²⁹Si-NMR.

EXAMPLE 2

[0140] General. The sodium lauryl sulfate was purchased from Proctor andGamble. The styrene was purchased from Sterling Chemical. The butylacrylate and ammonium hydroxide were purchased from Aldrich. Themethacrylic acid was purchased from Du Pont. The potassium persulfateand ammonium persulfate were purchased from FMC. All materials were usedas received without further purification.

[0141] Polymerization Procedure. To a 1 gal glass bowl reactor that hasbeen evacuate to less than 25 in Hg for 30 min add the Buffer Solutionand the Stage 1 Monomers. Heat to 170° F. and add the ActivatorSolution. Check the reactor solids after 30 min. If the solids are over18 wt % add ammonium hydroxide to yield a pH of 9.0. Remove a sample anddetermine its pH. If the pH is below 9.0 add additional ammoniumhydroxide. If solids are below 19 wt % continue the polymerization foran additional 30 min and recheck the polymer solids. The polymerizationwill overheat to 190° F.-200° F. (88° C.-93° C.). If overheating occursadjust the reactor temperature to 170° F. (77° C.)and begin adding theStage 2 Monomers. Adjust the flow rate so that the monomer is added overa period of 2.5 hours. Continue the polymerization at 170° F. (77° C.)until the residual styrene level drops below 500 ppm. If the residualstyrene remains above 500 ppm, add 0.1 parts of ammonium persulfate in200 ml of water and continue the polymerization until the residualstyrene is below 500 ppm. Allow the latex to cool before removing itfrom the reactor. Note that agitation should consist of 2 AFT's rotating200 rpm.

[0142] MEK Rub Testing Procedure. The latex material obtained in thepolymerizations was applied by brush on a block on non-porous masonryand allowed to cure at room temperature for 12 h. The resulting film wassubjected to methyl ethyl ketone (MEK) rub testing. Experiment 2a.Recipe: Buffer Solution RO Water: 1472.59 g Sodium Lauryl Sulfate (28%active): 3.35 g Stage 1 Monomers Styrene: 126.88 g Butyl Acrylate:235.63 g Methacrylic Acid: 37.50 g Activator Solution Water: 125 gPotassium Persulfate: 3.13 g Stage 2 Monomers Styrene: 297.50 g ButylAcrylate: 552.50 g Data/Results: Solids: 41.6 wt % pH: 8.40 BrookfieldViscosity: 20 MEK Rub Test (Reciprocations): 3 Experiment 2b. Recipe:Buffer Solution RO Water: 1472.59 g Sodium Lauryl Sulfate (28% active):3.35 g Stage 1 Monomers Styrene: 126.88 g Butyl Acrylate: 235.63 gMethacrylic Acid: 37.50 g Activator Solution Water: 125 g PotassiumPersulfate: 3.13 g Stage 2 Monomers Styrene: 293.75 g Butyl Acrylate:531.25 g The 3-methacryloxypropylsilane tri-acetal monomer fromExperiment 1c: 25.0 g Data/Results: Solids: 41.6 wt % pH: 8.44Brookfield Viscosity: 25 MEK Rub Test (Reciprocations): 35

EXAMPLE 3

[0143] General. All reagents were purchased from Alrich unless otherwisenoted and used without further purification. Tetrahydropyran-2-ol wasprepared according to the literature by the acid catalyzed hydrolysis ofdihydropyran (see Bartness J. E.; Hays R. L.; Caldwell G.; J. Am. Chem.Soc. 1981, 103, 1338 and March J. in Advanced Organic Chemistry, FourthEd., Wiley Interscience, N.Y.; p 764). All procedures were conductedunder nitrogen or in an inert atmosphere dry box using standard Schlencktechniques.

[0144] Experiment 3a. A solution of tetrahydropyran-2-ol (21 g, 0.21mol) in anhydrous diethyl ether (100 mL) was added dropwise to a slurryof NaH (4.7 g, 0.20 mol) in anhydrous diethyl ether (100 mL) withstirring at ca. 25° C. over a period of 2 hours. The resulting whiteprecipitate was filtered and washed with anhydrous diethyl ether (60mL), collected, and placed under vacuum until reaching a constantweight. The sodium salt of tetrahydropyran-2-ol (NaO-THP) was obtainedas a white solid in 86% yield and characterized by ¹H-NMR and ¹³C-NMR.

[0145] Experiment 3b. A solution of SiCl₄ (3.4 g, 0.02 mol) in anhydrousdiethyl ether (75 mL) was added dropwise to a slurry of NaO-THP (10 g,0.081 mol) in anhydrous diethyl ether (75 mL) with stirring at −78° C.over a period of 2 hours. The resulting heterogeneous mixture wasfiltered. The filtrate was collected and placed under vacuum untilreaching a constant weight. The silane tetra-acetal compound wasobtained as a colorless liquid and characterized by ¹H-NMR, ¹³C-NMR, and²⁹Si-NMR.

[0146] Variations in the present invention are possible in light of thedescription of it provided herein. While certain representativeembodiments and details have been shown for the purpose of illustratingthe subject invention, it will be apparent to those skilled in this artthat various changes and modifications can be made therein withoutdeparting from the scope of the subject invention. It is, therefore, tobe understood that changes can be made in the particular embodimentsdescribed which will be within the full intended scope of the inventionas defined by the following appended claims.

EXAMPLE 4

[0147] Experiment 4a (Polybutylacrylate)

[0148] Polybutylacrylate was prepared by emulsion polymerization in a 8oz glass bottle sealed with a screw cap which contained a rubber gasketand a Teflon liner. The soap solution for the polymerization wasprepared from 4.3 g dodecylbenzene sulfonic acid neutralized withammonium hydroxide in 150 g water treated by reverse osmosis. The soapsolution was charged to the bottle followed by 36 g of butylacrylate.Following the charging of the bottle, the head space was purged withnitrogen. The bottles were placed in a polymerization bath controlled ata temperature of 25° C. The bottle was allowed to rotate end-over-endfor 30 minutes to disperse the butylacrylate. After 30 minutes, 2 mls ofan activator solution containing 22 g of reverse osmosis water, 0.088 gferric sodium EDTA, and 0.194 g sodium formaldehyde sulfoxylate wascharged to the bottle through syringe and the bottle rotated. After 10minutes, 0.219 g of pinane hydroperoxide was charged to the bottle bysyringe to initiate the polymerization and allowed to rotate for 16hours.

[0149] Experiment 4b Polybutylacrylate-co-MethacryloxypropylTrimethoxysilane) ˜10 mole %

[0150] The same procedure employed as in Comparative Experiment 4a withthe only change being that 30.2 g butylacrylate and 5.9 gmethacryloxypropyl trimethoxysilane (A-174)were charged as the monomersolution.

[0151] Experiment 4c (Polybutylacrylate-co-MethacryloxypropylTrimethoxysilane) ˜5 mole %

[0152] The same procedure employed as in Comparative Experiment 4a withthe only change being that 32.8 g butylacrylate and 3.2 gmethacryloxypropyl trimethoxysilane (A-174)were charged as the monomersolution.

[0153] Experiment 4d (Polybutylacrylate-co-MethacryloxypropylTrimethoxysilane) ˜2.5 mole %

[0154] The same procedure employed as in Comparative Experiment 4a withthe only change being that 34.3 g butylacrylate and 1.7 gmethacryloxypropyl trimethoxysilane (A-174) were charged as the monomersolution.

[0155] Experiment 4e (Polybutylacrylate-co-Modified silane monomer) ˜10mole %

[0156] The same procedure employed as in Comparative Experiment 4a withthe only change being that 26.5 g butylacrylate and 9.5 g of thefollowing monomer were charged as the monomer solution.

[0157] Experiment 4f (Polybutylacrylate-co-protected A174) ˜5 mole %

[0158] The same procedure employed as in Comparative Experiment 4a withthe only change being that 30.5 g butylacrylate and 5.5 g of themodified silane containing monomer above were charged as the monomersolution.

[0159] Experiment 4g (Polybutylacrylate-co-protected A174) ˜2.5 mole %

[0160] The same procedure employed as in Comparative Experiment 4a withthe only change being that 33.05 g butylacrylate and 3.0 g of themodified silane containing monomer above were charged as the monomersolution.

[0161] Swelling Test

[0162] Latexes were cast on Teflon sheets and allowed to dry at roomtemperature for three days. Approximately 5 gms of the dried film wasplaced in 50 mls of toluene and allowed to reach an equilibrium weight.The ratio of the swollen weight to the initial weight was taken as apercentage to determine the degree of swelling of the films.

[0163] Aging test

[0164] The latex was aged by allowing to stand in a sealed bottle in anoven controlled at 50° C. for thirty days without agitation.

[0165] Polymerization Results Mole wt % n-BA wt % Silane % Silane %Conversion Experiment 4a 100 0 0 100 Experiment 4b 83.77 16.23 9.23 97.0Experiment 4c 91.17 8.83 4.83 98.0 Experiment 4d 95.39 4.61 2.55 98.9Experiment 4e 73.65 26.35 9.21 87.6 Experiment 4f 84.83 15.17 4.80 92.2Experiment 4g 91.81 8.19 2.32 94.1

[0166] As shown in the table, the conversion of the polymerizationsemploying the modified silane monomers were less (87%-94%) than thecomparative examples (97%-100%).

[0167] Swelling Results Mole % Silane Swelling wt % gain Experiment 4a 0Dissolved Experiment 4b 9.23 130 Experiment 4c 4.83 156 Experiment 4d2.55 278 Experiment 4e 9.21 236 Experiment 4f 4.80 259 Experiment 4g2.32 393

[0168] As expected, the degree of swelling decreases as the content ofthe silane monomers (A174, modified silane-containing monomer)decreases. It is expected that the difference in the degree of swellingat similar silane monomer loading levels is due to incompleteincorporation of the modified silane containing monomer.

[0169] Aging Results Swelling % wt Mole % Silane Swelling Time gainConversion Experiment 4b 9.23  0 days 130 15 days 276 30 days 238Experiment 4e 9.21  0 Days 226 15 days 184 30 days 145

[0170] The aging results demonstrate the inability of the A-174 monomerto remain stable in an aqueous environment for prolonged periods oftime. Initially, the degree of swelling increases indicating the loss offunctionality for crosslinking, likely by intra-particle crosslinking.At 30 days, the extent of crosslinking within the bottle is significantenough that the degree of swelling measurement is very dependent uponthe ability of the latex to form a cohesive film.

EXAMPLE 5

[0171] Adhesive Experimental

[0172] General. The following procedure was used to prepare the testsamples. The following modified silane reticulating agent waspredispersed in a mixture of Igepal CO-880 and 10 wt % NH₄OH:

[0173] Robond PS-94 was then added and the resulting mixture coated ontoa 2 mL polyester sheet using a 40 Mayer Rod. The coated sheets were thendried at 150° F. for 8 minutes. Igepal CO-880 was purchased from GAFCorporation. Robond PS-94 was obtained from Rohm and Haas Company. TestReticulating Igepal 10% Robond Sample Agent CO-880 NH₄OH PS-94 1   0 g0.12 g 3 g 50 g 2 0.66 g 0.12 g 3 g 50 g 3 1.3  0.24  6 g 50 g

[0174] All experiments were conducted under standard laboratoryconditions as set forth in ASTM D3924. The Probe Tack test was conductedaccording to ASTM D2979. The Peel Adhesion test was performed usingstainless steel and was conducted according to PSTC-1. The ShearAdhesion Failure Temperature test was performed using stainless steeland was conducted according to PSTC Appendage B. The modified silanereticulating agent was prepared using the same procedure as Example 3,Experiment 3b with the following changes. A solution ofbis(trichlorosilyl)octane (23.25 g, 0.061 mol) in anhydrous diethylether (200 mL) was added dropwise to a slurry of NaO-THP (50.49 g,0.3661 mol) in anhydrous diethyl ether (200 mL) with stirring at −78° C.over a period of 2 hours. The resulting heterogeneous mixture wasfiltered. The filtrate was collected and placed under vacuum untilreaching a constant weight. The modified silane reticulating agent wasobtained as a vicous liquid and characterized by ¹H-NMR, ¹³C-NMR, and²⁹Si-NMR.

[0175] Results.

[0176] Probe Tack: Test Polyken Probe Tack (grams) S Sample 1 2 3 4 5 6Ave Deviation 1 657 617 624 676 634 599 635 27.9 2 567 564 529 589 575600 571 24.5 3 547 487 509 516 479 451 498 33.3

[0177] These test results show that the modified silane reticulatingagent reduces tack in increasing amount, thus demonstrating increasedcure and crosslinking over the control sample which did not contain themodified silane reticulating agent.

[0178] Experiment Peel Adhesion: PSTC-1 Peel Adhesion Test (lbs/inchwidth) Sample 1 2 3 Average S Deviation 1 1.69 1.54 1.50 1.58 0.10 21.84 1.85 1.88 1.86 0.02 3 1.99 1.85 1.87 1.90 0.08

[0179] These test results show that the modified silane reticulatingagent increases adhesion, in increasing amount compared to the controlsample which did not contain the modified silane reticulating agent.

[0180] Shear Adhesion Failure Temperature: Test Shear Adhesion FailureTemperature (deg F.) Sample 1 2 Average S Deviation 1 267.0 266.0 266.50.7 2 >400 >400 >400 0.0 3 259.0 261.0 260.0 1.4

[0181] These test results show that the modified silane reticulatingagent increases the temperature at which adhesion failure occurs andfurther shows that this property is only improved at lower levels of themodified silane reticulating agent.

What is claimed is:
 1. A polymer which is comprised of polymer chainshaving at least one modified silane moiety bonded thereto, wherein saidmodified silane moiety is of a structural formula selected from thegroup consisting of:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X″ groups can be the same or different; wherein X″represents a chemical moiety; wherein R, R′, and R″ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.
 2. A polymer as specified in claim 1wherein the modified silane moiety is of the structural formula:


3. A polymer as specified in claim 1 wherein the modified silane moietyis of the structural formula:


4. A polymer as specified in claim 1 wherein the modified silane moietyis of the structural formula:


5. A polymer as specified in claim 1 wherein the modified silane moietyis of the structural formula:


6. A polymer as specified in claim 2 wherein Y is oxygen and Z isC(R)R′.
 7. A polymer as specified in claim 2 wherein Z is oxygen and Yis C(R)R′.
 8. A polymer as specified in claim 3 wherein Y is oxygen andZ is C(R)R′.
 9. A polymer as specified in claim 3 wherein Z is oxygenand Y is C(R)R′.
 10. A polymer as specified in claim 4 wherein Y isoxygen and Z is C(R)R′.
 11. A polymer as specified in claim 4 wherein Zis oxygen and Y is C(R)R′.
 12. A polymer as specified in claim 5 whereinY is oxygen.
 13. A polymer as specified in claim 2 wherein the monomeris of the structural formula:

wherein X″ groups can be the same or different; wherein X″ represents achemical moiety.
 14. A polymer as specified in claim 13 wherein n is 3.15. A polymer as specified in claim 1 wherein at least one memberselected from the group consisting of R, R′ and R″ is a hydrogen atom.16. A polymer as specified in claim 13 wherein n is
 2. 17. A polymer asspecified in claim 13 wherein n is
 1. 18. A polymer as specified inclaim 2 wherein n is
 3. 19. A polymer as specified in claim 3 wherein nis
 3. 20. A polymer as specified in claim 4 wherein n is 3.